CN101830092A - Method for preparing corrosion-resistant colored decorative film - Google Patents
Method for preparing corrosion-resistant colored decorative film Download PDFInfo
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- CN101830092A CN101830092A CN200910111245A CN200910111245A CN101830092A CN 101830092 A CN101830092 A CN 101830092A CN 200910111245 A CN200910111245 A CN 200910111245A CN 200910111245 A CN200910111245 A CN 200910111245A CN 101830092 A CN101830092 A CN 101830092A
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Abstract
The invention relates to a corrosion-resistant colored decorative film and a preparation method thereof. The method prepares the corrosion-resistant colored decorative film on the surface of a metal material by adopting radio-frequency magnetron sputtering technology, and the prepared decorative film has good bonding force with a substrate. The metal material is zinc, copper, aluminum or alloy of the metals. The decorative film prepared by the method has a double-layer film structure, wherein the first layer is a titanium film, and the second layer is a (carbonized or azotized) titanium film. The method can prepare the acid, alkali and corrosion resistant decorative film with different colors comprising golden yellow, purple, dark blue, silvery white, black and the like. The method has the advantages of no environmental pollution, simple operation, low cost and capability of large-scale production; the prepared film has high quality; and the method is suitable for preparing the decorative film by using the metal material or the similar metal material as a base material.
Description
Technical field
The present invention relates to a kind of preparation method of corrosion-resistant colored decorative film, belong to material surface preservative treatment, decorating film technical field.
Background technology
Traditionally, the following two kinds of methods of the general employing of decorating film strengthen the Corrosion Protection of ornaments and the color of regulating ornaments: 1, at surface of decoration chromium plating, nickel, aluminium, silver or golden film, the decorating film of this method preparation has metallic luster, help improving the grade of ornament, and can improve the Corrosion Protection of ornament to a certain extent, but the color of metallic film is more single, generally all be golden yellow, silvery white metallic luster, the ornament that obtain other surface color is relatively more difficult; 2, has the coating of different colours by be coated with organic polymer etc. at surface of decoration, though it is also relatively good that this method can obtain the decorating film and the Corrosion Protection of multiple color, but the paint metal glossiness is relatively poor, improve the product bit comparison difficulty of ornament, and coating is easily aging and make that ornament fades, Corrosion Protection weakens.
Can significantly improve the hardness and the Corrosion Protection of ornament at surface deposition titanium nitride, titanium carbide or titanium carbonitride one class ganoine thin film.The method of disclosed in recent years this class decorating film of preparation has ion plating (CN2398655Y), electrophoresis (CN 101109097A), chemical vapour deposition (CVD) (CN 1623008A, CN1898410A) and magnetron sputtering (CN 2254448Y) etc.These methods mainly still concentrate on and solve solid color depositing of thin film technology, improve problems such as film quality at present; Therefore, thus explore novel thin film deposition processes and prepare the market competitiveness that good, the corrosion-resistant and decorating films various different colours that hardness is big, anti-wear performance is good of adhesive force help improving ornament.It is the titanium carbonitride film multi-layer film structure that the surface of decoration of substrate has prepared gold, purple, brown, rifle look and black at iron, copper, steel, aluminium and aluminium alloy that publication CN 1055957A adopts ion electroplating method.This patent has solved the problem of preparation different colours decorating film, but the multi-layer film structure that this decorating film is taked too complicated (～6 layers), and also the deposition process parameters of each tunic is different, influenced applying of this method.
The present invention uses radiofrequency magnetron sputtering technology, the design double membrane structure, the proportioning of adopt the titanium target, regulating working gas in the film deposition process, thereby the decorating film of different colours such as the golden yellow of preparing, purple, navy blue, silvery white, black and acid-alkali-corrosive-resisting.Be intended to simplify the depositing operation of existing colored decorative film, promote the application of the type decorating film.
Summary of the invention
The present invention levies and current ion plating, electrophoresis, chemical vapour deposition (CVD) and magnetron sputtering method are prepared decorating film has problems such as the single or colorful film depositing operation complexity of color, double membrane structure is proposed, simplify the preparation technology of the type decorating film, realized that simple process prepares the decorating film of different colours, acid-alkali-corrosive-resisting.
The present invention uses radiofrequency magnetron sputtering technology, adopt titanium target and argon gas, nitrogen and acetylene gas mixture to carry out reactive sputtering, prepared the decorating film of the different color of golden yellow, purple, navy blue, silvery white, black depth curve in the metal substrate surface that constitutes by zinc, copper, aluminium or these metals alloy between mutually, employed titanium target purity is not less than 99%, and relative density is not less than 0.90.
The decorating film of the present invention's preparation is a double membrane structure, and ground floor is a titanium film, and the second layer is titanium carbonitride film, titanium nitride film or titanium carbonitride film.This decorating film ability strong acid, alkali corrosion.
The corrosion-resistant colored decorative film of the present invention's preparation, different colours decorating film deposition process satisfies following preferred processing condition:
Ground floor: working gas is an argon gas, and operating pressure is 0.3～0.6Pa, and titanium target sputtering power is 100W, and base reservoir temperature is 100～400 ℃, and bias voltage is-100V that film thickness is 20～50nm.
The second layer: depositing operation such as following table:
The decorating film of the present invention preparation has multiple color, present characteristics such as the metallic luster of light and thickness be accurate, and technology is simple, depositing temperature is low, helps applying.
Description of drawings
Accompanying drawing is the decorating film structural representation of radio-frequency magnetron sputter method preparation, and wherein: 1 is that (carbon, nitrogen) changes titanium film, and 2 is titanium film, and 3 are substrate.
The specific embodiment
Embodiment 1: rf magnetron sputtering prepares golden yellow corrosion-resistant decorating film.
Sputter is 99.9% with titanium target purity, relative density is～and 0.90.The titanium target correctly is installed on (as shown in Figure 1) in the target rifle, and adjusting target rifle and vertical direction angle is～30 °, is evacuated to vacuum chamber base vacuum degree and is higher than 2.0 * 10
-4Pa.(the ratio Cu of atomicity: Zn=6: 4) ornament is substrate, and base reservoir temperature is 400 ℃ with ormolu.
The first tunic depositing operation: in vacuum chamber, feed 20sccm (sccm represents standard milliliter per minute) argon gas, regulating the interior pressure of vacuum chamber is 0.5Pa, regulating bias voltage is-100V, the sample slewing rate is 10 rev/mins, the radio-frequency power supply power adjusting is 100W, the control sedimentation time is 5min, at the about 30nm of titanium film thickness of this condition deposit.
The second tunic depositing operation: the work atmosphere in the vacuum chamber is changed into 25sccm argon gas, 2sccm nitrogen and 2sccm acetylene, and the adjusting pressure in vacuum tank is 0.5Pa, and regulating radio-frequency power supply power is 150W, and it is consistent with previous step that all the other conditions keep.At this condition deposit 60min, film thickness is about 1 μ m, and the decorating film color is for golden yellow and have metallic luster.
Embodiment 2: rf magnetron sputtering prepares the corrosion-resistant decorating film of purple.
(the ratio Cu of atomicity: Zn=6: 4) ornament is substrate, and base reservoir temperature is 200 ℃, and all the other are with embodiment 1 with ormolu.
The first tunic deposition process conditions is with embodiment 1.
The second tunic deposition process conditions is: work atmosphere is 25sccm argon gas, 2sccm nitrogen and 4sccm acetylene; Operating pressure is 0.5Pa; Radio-frequency power supply power is 100W; All the other deposition process conditions are with embodiment 1.At this condition deposit 60min, decorating film thickness is about 700nm, and color is purple and has metallic luster.
Embodiment 3: rf magnetron sputtering prepares the corrosion-resistant decorating film of navy blue.
(the ratio Zn of atomicity: Al=9: 1) ornament is substrate, and base reservoir temperature is 200 ℃, and all the other are with embodiment 1 with allumen.
The first tunic deposition process conditions is with embodiment 1.
The second tunic deposition process conditions is: work atmosphere is 20sccm argon gas and 20sccm nitrogen; Operating pressure is 0.4Pa; Radio-frequency power supply power is 180W; All the other deposition process conditions are with embodiment 1.At this condition deposit 60min, decorating film thickness is about 1.2 μ m, and color is navy blue and has metallic luster.
Embodiment 4: rf magnetron sputtering prepares silvery white corrosion-resistant decorating film.
(the ratio Cu of atomicity: Zn=6: 4) ornament is substrate, and base reservoir temperature is 200 ℃, and all the other are with embodiment 1 with ormolu.
The first tunic deposition process conditions is with embodiment 1.
The second tunic deposition process conditions is: work atmosphere is 30sccm argon gas and 2sccm acetylene; Operating pressure is 0.3Pa; Radio-frequency power supply power is 150W; All the other deposition process conditions are with embodiment 1.At this condition deposit 60min, decorating film thickness is about 1.2 μ m, and color is for silvery white and have metallic luster.
Embodiment 5: rf magnetron sputtering prepares the corrosion-resistant decorating film of black.
(the ratio Zn of atomicity: Al=9: 1) ornament is substrate, and base reservoir temperature is 350 ℃, and all the other are with embodiment 1 with allumen.
The first tunic deposition process conditions is with embodiment 1.
The second tunic deposition process conditions is: work atmosphere is 30sccm argon gas and 3sccm acetylene; Operating pressure is 0.5Pa; Radio-frequency power supply power is 100W; All the other deposition process conditions are with embodiment 1.At this condition deposit 60min, decorating film thickness is about 650nm, and color is black and has metallic luster.
Embodiment 6: the performance test of decorating film acid-alkali-corrosive-resisting.
5 kinds of decorating films of embodiment 1～embodiment 5 preparations are placed the H of variable concentrations respectively
2SO
4With soak the sample observation decorating film surface gloss before contrast is soaked after cleaning again, integrality etc. in the NaOH solution.The H that uses in the experiment
2SO
4Concentration is respectively 98%, 50%, 5% and 1%, and NaOH concentration is respectively 25mol/l, 10mol/l, 5mol/l, 1mol/l and 0.1mol/l, and soak time is 120min.Sample after the above-mentioned immersion finds that surface gloss, integrality do not change after cleaning paired observation, not by the vestige of acid and alkali corrosion, illustrate that this decorating film can acid-alkali-corrosive-resisting.
Claims (3)
1. corrosion-resistant colored decorative film is characterized in that: substrate is made of zinc, copper, aluminium or these metals alloy between mutually; Decorating film is a double membrane structure, and ground floor is a titanium film, and the second layer is titanium carbonitride film, titanium nitride film or titanium carbonitride film.
2. the described decorating film of claim 1, it is characterized in that: this colored decorative film has the different color of golden yellow, purple, navy blue, silvery white or black, and acid-alkali-corrosive-resisting.
3. the preparation method of claim 1 or 2 described colored decorative films is characterized in that: adopt the titanium target to prepare through radiofrequency magnetron sputtering technology; Employed titanium target purity is not less than 99%, and relative density is not less than 0.90; Working gas is argon gas, nitrogen and acetylene.
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| CN200910111245A CN101830092A (en) | 2009-03-13 | 2009-03-13 | Method for preparing corrosion-resistant colored decorative film |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206800A (en) * | 2011-04-28 | 2011-10-05 | 中南大学 | Ion beam sputtering method for preparing golden yellow decorative film, and film |
| CN102465253A (en) * | 2010-11-05 | 2012-05-23 | 鸿富锦精密工业（深圳）有限公司 | Vacuum film plating piece and manufacturing method thereof |
| CN102548310A (en) * | 2010-12-24 | 2012-07-04 | 鸿富锦精密工业（深圳）有限公司 | Shell and manufacturing method thereof |
| CN102595834A (en) * | 2011-01-18 | 2012-07-18 | 鸿富锦精密工业（深圳）有限公司 | Shell body and manufacturing method thereof |
| CN102595833A (en) * | 2011-01-05 | 2012-07-18 | 鸿富锦精密工业（深圳）有限公司 | Aluminum or aluminum alloy shell and manufacturing method thereof |
| CN102644047A (en) * | 2011-02-18 | 2012-08-22 | 鸿富锦精密工业（深圳）有限公司 | Shell and manufacturing method thereof |
| CN102719789A (en) * | 2012-06-18 | 2012-10-10 | 东莞劲胜精密组件股份有限公司 | Composite film and film plating method thereof |
| CN102744926A (en) * | 2012-06-20 | 2012-10-24 | 中国科学院宁波材料技术与工程研究所 | Colorful anticorrosion decorative film with controllable surface color of matrix and preparation method thereof |
| CN102766845A (en) * | 2012-07-09 | 2012-11-07 | 珠海承鸥卫浴用品有限公司 | Metal surface PVD (Physical Vapor Deposition) decorative coating method |
| CN103088289A (en) * | 2011-10-31 | 2013-05-08 | 深圳富泰宏精密工业有限公司 | Shell making method, and shell made through method |
| CN103305802A (en) * | 2013-07-05 | 2013-09-18 | 北京东明兴业科技有限公司 | PVD (Physical Vapor Deposition) film on electronic product metal surface and preparation method thereof |
| CN103935075A (en) * | 2013-01-23 | 2014-07-23 | 深圳富泰宏精密工业有限公司 | Shell and manufacturing method thereof |
| CN104032277A (en) * | 2014-06-25 | 2014-09-10 | 广州万尔真空科技有限公司 | Method for surface treatment of golf club head by using black-figure compound coating |
| CN104441841A (en) * | 2014-11-03 | 2015-03-25 | 肇庆市振华真空机械有限公司 | Gold-imitation coated glass and preparation technology thereof |
| CN107587108A (en) * | 2017-08-09 | 2018-01-16 | 广东欧珀移动通信有限公司 | The processing method of terminal, the housing of terminal and housing |
| CN108004505A (en) * | 2017-12-26 | 2018-05-08 | 江苏蔚联机械股份有限公司 | A kind of screen color ornamental strip with metallic luster and preparation method thereof |
| CN113621914A (en) * | 2020-05-06 | 2021-11-09 | 华为机器有限公司 | Silvery white coating and preparation method thereof |
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| US4226082A (en) * | 1976-06-07 | 1980-10-07 | Nobuo Nishida | Ornamental part for watches and method of producing the same |
| GB2226334A (en) * | 1988-11-25 | 1990-06-27 | Atomic Energy Authority Uk | Multilayer coatings |
| EP0416887A2 (en) * | 1989-09-08 | 1991-03-13 | Nippon Steel Corporation | Ceramic-coated metal sheet |
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Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102465253A (en) * | 2010-11-05 | 2012-05-23 | 鸿富锦精密工业（深圳）有限公司 | Vacuum film plating piece and manufacturing method thereof |
| CN102548310A (en) * | 2010-12-24 | 2012-07-04 | 鸿富锦精密工业（深圳）有限公司 | Shell and manufacturing method thereof |
| CN102595833A (en) * | 2011-01-05 | 2012-07-18 | 鸿富锦精密工业（深圳）有限公司 | Aluminum or aluminum alloy shell and manufacturing method thereof |
| CN102595834A (en) * | 2011-01-18 | 2012-07-18 | 鸿富锦精密工业（深圳）有限公司 | Shell body and manufacturing method thereof |
| CN102644047A (en) * | 2011-02-18 | 2012-08-22 | 鸿富锦精密工业（深圳）有限公司 | Shell and manufacturing method thereof |
| CN102206800A (en) * | 2011-04-28 | 2011-10-05 | 中南大学 | Ion beam sputtering method for preparing golden yellow decorative film, and film |
| CN103088289A (en) * | 2011-10-31 | 2013-05-08 | 深圳富泰宏精密工业有限公司 | Shell making method, and shell made through method |
| CN102719789A (en) * | 2012-06-18 | 2012-10-10 | 东莞劲胜精密组件股份有限公司 | Composite film and film plating method thereof |
| CN102719789B (en) * | 2012-06-18 | 2014-05-21 | 东莞劲胜精密组件股份有限公司 | Composite film and film plating method thereof |
| CN102744926A (en) * | 2012-06-20 | 2012-10-24 | 中国科学院宁波材料技术与工程研究所 | Colorful anticorrosion decorative film with controllable surface color of matrix and preparation method thereof |
| CN102766845A (en) * | 2012-07-09 | 2012-11-07 | 珠海承鸥卫浴用品有限公司 | Metal surface PVD (Physical Vapor Deposition) decorative coating method |
| CN102766845B (en) * | 2012-07-09 | 2015-02-25 | 珠海承鸥卫浴用品有限公司 | Metal surface PVD (Physical Vapor Deposition) decorative coating method |
| CN103935075A (en) * | 2013-01-23 | 2014-07-23 | 深圳富泰宏精密工业有限公司 | Shell and manufacturing method thereof |
| CN103935075B (en) * | 2013-01-23 | 2018-07-03 | 深圳富泰宏精密工业有限公司 | Housing and preparation method thereof |
| CN103305802A (en) * | 2013-07-05 | 2013-09-18 | 北京东明兴业科技有限公司 | PVD (Physical Vapor Deposition) film on electronic product metal surface and preparation method thereof |
| CN103305802B (en) * | 2013-07-05 | 2015-09-30 | 东明兴业科技股份有限公司 | Electronic product metallic surface PVD film and preparation method thereof |
| CN104032277A (en) * | 2014-06-25 | 2014-09-10 | 广州万尔真空科技有限公司 | Method for surface treatment of golf club head by using black-figure compound coating |
| CN104441841A (en) * | 2014-11-03 | 2015-03-25 | 肇庆市振华真空机械有限公司 | Gold-imitation coated glass and preparation technology thereof |
| CN104441841B (en) * | 2014-11-03 | 2017-02-15 | 广东振华科技股份有限公司 | Gold-imitation coated glass and preparation technology thereof |
| CN107587108A (en) * | 2017-08-09 | 2018-01-16 | 广东欧珀移动通信有限公司 | The processing method of terminal, the housing of terminal and housing |
| CN108004505A (en) * | 2017-12-26 | 2018-05-08 | 江苏蔚联机械股份有限公司 | A kind of screen color ornamental strip with metallic luster and preparation method thereof |
| CN113621914A (en) * | 2020-05-06 | 2021-11-09 | 华为机器有限公司 | Silvery white coating and preparation method thereof |
| CN113621914B (en) * | 2020-05-06 | 2024-04-26 | 华为机器有限公司 | Silvery white coating and preparation method thereof |
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Application publication date: 20100915 |